DE1719381A1 - Disazo dyes, process for their preparation and their use - Google Patents

Description

CIBA AKTIENGESELLSCHAFT, BASEL (SWITZERLAND)

Germany

Disazo dyes ,, process for their preparation and their

Use.

The present application relates to new, valuable ones Disazo dyes in which two monoazo dye molecules

of general type .. '' yy

^ ^R l
DN = NA-NCT (I)

* 2

wherein D is the remainder of a mono- or bicyclic diazo component, A is a p-phenylene radical and R-, and R each optionally substituted alkyl radical, via its coupling components through a divalent bridge Z, without dye character are linked, with at least one of the monoazo dye residues directly on the aromatic nucleus A, optionally via a nucleus-bound alkylene bridge, with the divalent radical Z

109817/1971

is linked, and the group Z when D is a heterocyclic System, and Z represents two oxygen atoms directly connected to the phenylene radicals A or two via the Nitrogen atom directly connected to the phenylene radicals A contains carboxamide groups, either at the same time an unsaturated, aromatic or heterocyclic radical or one through at least one heteroatom contains interrupted carbon chain · * The invention therefore relates, for example, to

new disazo dyes of the general formula

R.

- * r

x-1

(II)

- (■ alkylene)

r — 1 12

M R /> *

wherein R, R_, R ^ and Rj. each have a hydrogen atom or optionally substituted

preferably / alkyl groups, where, when χ = 2, R_ can be linked to the radical A ₂ to form a ring, Rl is an alkylene group, q, r and χ each have an integer of 1 or 2, A ₁ and A each a phenylene radical to which the azo group

and the group -

respectively. -

in 1,4-position to each other

stand, D-, and / or D _? any residue of an optionally quaternized diazo component and Z is a divalent bridge

109317/197 1

• ■ ■

-3 -

member without dye character means, where, when χ = 1, q = 1 and r = 1 and the radicals D and Dp each represent a heterocyclic system and Z two oxygen atoms _{or two directly connected to the aromatic radicals A. and A p} Contains carboxamide groups linked via the nitrogen atom, the bridge member Z at the same time either an unsaturated, aromatic or heterocyclic ^

"■■ '■■■ ⁴ I.

Contains a radical or a carbon chain interrupted by at least one heteroatom; the mixtures of the new disazo dyes among themselves and their mixtures with other azo dyes, especially monoazo dyes, are also Subject of the invention.

The present invention therefore encompasses both disazo dyes of the formula

D —N = NA —f alkyl Z — R '
R ₁

where D ₁ , D ₂ , Α _χ , Ag ₃ -R ₁ ', R _g , R ,, R ^ and q have the same meaning as in formula (II) and Z. is a divalent bridge member without dye character, as well as dyes the formula

109817/1971

-A- (alkylene) - ^ - (alkylene) ^ -

N N

^ R ₃ R ₃ R ₄

wherein D ₁ , D ₃ , R ₁ , R ^, R ,, R ^, A ₁ , A ₃ , q and r have the same meaning as in formula (II), and Z is a divalent bridge member without dye character, where, when q = 1 and r = 1, and the radicals D, and D _p each represent a heterocyclic system and Z contains two _{oxygen atoms directly connected to the aromatic radicals A and A p} or two carboxamide groups connected via the nitrogen atom, the bridging member Z at the same time contains either an unsaturated, aromatic or heterocyclic radical or a carbon chain interrupted by at least one heteroatom.

The alkylene groups via which Z can be linked to the radicals A and A are preferably methylene or ethylene groups. D ₁ and D can be the same or different

Preferably the pairs of substituents have R, and

R-. as well as R and R ^. each have the same meaning, while 'groups A-. and A _{p is} preferably radicals of the formulas

109817/1971

? i

- \ ~~ V- imd

mean, where c ^ c ^, d-, and d hydrogen atoms, methyl-, Ethyl, methoxy, ethoxy, pherrylthio or phenoxy radicals

■ -. '■' ■■ -; ■■ '

are.

The groups c, and Cp are preferably in ortho position to the azo group and in addition to the groups mentioned above, a chlorine or bromine atom, a trifluoromethyl group, an alkylsulfonyl, preferably a methylsulfonyl group, and one optionally mean acylamino group alkylated on the nitrogen atom, preferably methylated, in which the acyl radical the remainder of an organic monocarboxylic acid, an organic monosulfonic acid, such as methane, ethane or p-toluene monosulfonic acid, or the remainder of a carbamic acid or a carbonic acid monoester or monoamide such as phenoxycarbonyl, methoxycarbonyl and aminocarbonyl.

The groups d-, and d are preferably in ortho to the coupling-directing amino group bound.

If the group R is connected to the group A _p in the ortho position to form a ring, tetrahydroquinoline or benzmorpholine radicals are present, for example.

1 0 98 1 7/197 1

The groups R and Rp can be hydrogen atoms or lower, i.e. 1 to 4, preferably 2 to 4 carbon atoms containing alkyl groups, such as methyl, ethyl, n-propyl or n-butyl groups, which in the usual way - can be substituted, such as halogenated alkyl groups, such as ß-chloroethyl, β, β, β-trifluoroethyl, ß, 7 ~ Diehlorpropyl-, ß-cyanoethyl, alkoxyalkyl, such as ß-ethoxyethyl or ^ -Methoxybutyl, hydroxyalkyl, such as ß-hydroxyethyl, ß, 7-dihydroxypropyl, nitroalkyl, such as ß-mitroethyl, carbalkoxy, such as ß-carbo (methoxy, ättioxy or propoxy) ethyl (where the terminal alkyl group In to position Can carry cyano, carbalkoxy, acyloxy and amino groups), ß- or 7-carbo (methoxy or ethoxy) propyl, Acylaminoalkyl, such as ß- (acetyl or formylJ-amino-ethyl, Acyloxyalkyl, such as ß-acetyloxyethyl, ßj'y-diacetoxypropyl, ß- (alkyl or aryl) sulfonylalkyl, such as ß-methanesulfonylethyl, ß-ethanesulfonylethyl or ß-Cp-chlorobenzenesulfonyl) ethyl, Alkyl or Arylcarbamoyloxyalkyl-, such as ß-Methylcarbamyloxyäthyl- and ß-Phenylcarbamyloxyäthyl-, Alkyloxycarbonyloxyalkyl-, like ß- (methoxy-, ethoxy- or isopropyloxy) -carbonyloxyäthyl-, 7-acetamidopropyl-, ß- (p-nitrophenoxy) -ethyl-, ß- (p-hydroxyphenoxy) -ethyl-, ß- {ß'-acetylethoxycarbonyl) -ethyl-, ß- [ß '- (cyano-, hydroxy-, methoxy- or acetoxyJ-ethoxycarbonyl-ethyl-, cyanoalkoxyalkyl-, ß-carboxyethyl, ß-acetylethyl, ^ -amnopropyl, ß-diethylaminoethyl, β-Cyanacetoxyäthyl- and ß-Benzoyl-ß- (p-alkoxy-

109817/1971

or phenoxy-benzoyl) -oxyethyl groups. These groups generally contain no more than nine carbon atoms.

The groups R ,, R ₁ . and Rl can have the same substituents as the groups R ₁ and R _p .

Groups of the following formulas come into consideration as the colorless bridge member Z: -S-, -SS-, -NH-, -N-, -SO-, -SQ ₂ -, -CO- and in particular

Groups of the formula -X ' -R ₁ . -X'-, where X ^{1 is} an oxygen atom, a sulfur atom or an NH group, the hydrogen atom of which can optionally be substituted by an alkyl group with up to 4 carbon atoms, in particular a methyl group, and R ₁ - a divalent aliphatic, cycloaliphatic, araliphatic, is an aromatic or heterocyclic radical whose carbon chain can be interrupted by heteroatoms, in particular oxygen atoms, and which, if both diazo components are heterocyclic ring systems and / or X 'is an oxygen atom, is preferably not a polymethylene chain. The radicals R ₁ are particularly preferred. of the formulas -CH-CH-,

D 2 2

-, '-CH ₂ -CH ₂ -X' -CHg-CHg-, like -

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-OH ₂

and especially the acyl radical-containing groups of the formulas -OCO-, -OCOO-, OCOCOO-, -NHCO-, -CONH-, -CONHCO-, -CONHNHCO-, -NHCOCONH-, -O-CHg-CO-O-alkylene -O-CO-CHg-O-. Z can also have the formula -X ¹ CO-Rg-COX L, where X ^{1 is} an oxygen atom, a sulfur atom or an -NH- group, which can be substituted as indicated above, and IL-. is an aliphatic, aromatic or heterocyclic radical, preferably an ethylene or a p-, m- or o-phenylene radical, or correspond to the formula -X'-CO-NH-R ₇ -NH-CO-X-, in which X ¹ an oxygen atom, a sulfur atom or an NH group and R ₇ an aliphatic, aromatic or heterocyclic radical of a diisocyanate, preferably an ethylene, hexamethylene, p-phenylene or toluylene radical, a radical of the formula

is. Finally, in certain cases, Z also corresponds to the formula -OCOX ¹ -Rg-X ¹ OCO-, where X 'has the same meaning as

109817/1971

and Ro is a divalent organic radical, in particular an aliphatic araliphatic aromatic or heterocyclic radical, which can be interrupted by the groups X '(if X ^{f is} an NH group, Rn has the same meaning as R ₇ ) or the formula

-X "SO -R -SO X" -, where X "is an oxygen atom or an optionally substituted nitrogen atom and R _{Q is} an aliphatic or aromatic radical.

You can use the new dyes. get if you either
a) two coupling components A-Nv _n ^ » by one

divalent bridge Z without dye character to one another are linked and at least one of which is linked directly to the aromatic nucleus A, optionally via a nucleus-bound Alkylene bridge is bonded to the radical Z, with diazo compounds from amines D, -ΝΗ ~ and Dp-NEL · to disazo compounds Couples, where the symbols A, Z, R ,, Rp, D, and D_ the above have given meaning, or that one b) two identical or different dyes of the formula

DN = NA ₁ -NC

in which D and R have the meaning given, A _{1 is} a 1,4-phenylene radical and R _{x is} an optionally substituted alkyl group or a hydrogen atom and in one of the radicals A and R- is a convertible substituent

109817/1971

- ίο -

is present, with the remainder Z donating compounds implemented at the same time in one stage or successively in two stages.

I. Process variant a)
A. Coupling components:

Coupling components for embodiment a) of the process are preferably those of formula

(Alkylene)

^R 4

A ₂
N

R / N

x-1

2-x

where A _± ,

^, R ₁ , R ₃ , R, R ^, R ^, Z, r, q and χ have the same meaning as above, for example the diamines of the formula

[—A, - (alkylene)

- ^

I.
- (alkylene) ^^ - A ₂ -]

10 9817/1971

-u -

wherein R ₁ * Rp, R 'and R ^, A ,, A, Z, q and r have the same meaning as in formula IV, and the bifunctional coupling components of the general formula

H
- ¹

- (iÜJkylenl-γ-Ζ — R '

R ₂

wherein the symbols q, A ₁ , A ^, R ₁ , R ₂ , Ry R ^ and Z have the same meaning as in formula II; they are obtained, for example, as follows:

If, for example, (I) - N-hydroxyethyl-N-cyanoethyl-aniline is used with phosgene to form carbonic acid ester, and (2) m-nitroaniline with ethylene oxide is used N, N-di- (hydroxyethyl) -m-nitroaniline, acetylated on the hydroxyethyl groups and finally hydrogenated the m-nitro group to the m-amino group, the condensation of the 4-amino-N, N-di (acetoxyethyl) aniline obtained with the Chlorocarbonic acid ester is the bifunctional coupling component of the formula

C ₉ H.CN
^{Z 4} <r> -NiCH CH GC-CH,) ₂

⁴ Il 0

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If 3-nitrophenyl isocyanate is used with N-hydroxy-ethyl-N-cyanoethyl-aniline to reduce the resulting carbamine 'acid ester on the 3-nitro group and if the 3-amino group formed is reacted with acrylonitrile, one obtains

the following b ^ functional coupling components of the J

formula

V ₄

A bifunctional coupling component is obtained by condensing N-chloroethyl-N-ethyl-aniline with 3-nitrophenol to form the phenol ether, then reducing the 3 ~ ^s nitro group of the phenol ether to the 3-amino group and adding 1 molecule of acrylonitrile to the 3-amino group the following formula

NHC ₂ H CN

109817 / Ί971

1718381

If one adds a mole of -2,4-diisocyanate-toluene with the active one ^ -Isocyanato group on one mole of N-ethyl-N-hydroxyäthyl-anilinj a compound with a free 2-isocyanato group is thus obtained by addition of NjN-bis-ß-acetoxyäthyl ^ -aminoaniline the bifunctional coupling component of the formula is obtained on the free 2-isocyanato group

C ₀ H.

■ Νϊ _O H - ■ Ο — Ο-ΝΗ-ιΛ Il

⁴ II U-CH, CH ₀ CH ₀ OCCH

O A ³ <~> N ^{/ 2 2}

- CO— ISfBr

Suitable bifunctional coupling components for the reaction with the diazonium compounds from the amines of the formula D-, -NHp and / or Dp-NHp sirü also the following compounds / which, however, are preferably not coupled with heterocyclic and / or quaternizable coupling components, and those other than the groups -NR ₁ R, and -NRpR _{21- must} not contain any further coupling-directing groups attached to the aromatic nucleus.

10 9817/1971

Other suitable bifunctional coupling components, which form an object of the invention are the compounds of the formulas:

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O C = O

C = O

I 0

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so

NH

NH

SO ₀

R N

C = O

NH

CH.

NH

C = O

(CH ₂ ) ₂

SO,

I like that

R ₁

. _Ν Λ

C = O

NH

NH

I.
C = O

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CH ₂ C = O

(CH ₂ ) ₂

C = O OH ₂

- 17 - 0
I. 0
J R ₁ 2 4th R _n CH ₂ C = O
I. I.
C = O
I. I.
I ² I.
0 C = O
I. (CH ₂ ) ₂ -O- I.
? <d> -Ϊ I.
C = O

R _n

0 C = O (CH ₀ ).

C = O

R.

l /

C = O

NH

2 ^J 6

(CH ₀ ) NH

C = O 0

0 °

C = O
X ¹

(alkylene) X ¹

C = O

• IP

r / -2

1 0 9 8 17/1971

wherein X ^{1 represents} an NH group, an oxygen atom or a sulfur atom.

If the construction of the bifunctional coupling components is based on o-nitrobenzenesulfonic acids or carboxylic acids, or from their reactive derivatives, such as, for example, nitrobenzenesulfonic acid chloride, the sulfonic acid or carboxylic acid groups are connected to one another, for example by a diamide group, then after subsequent hydrogenation of the nitro groups and N-alkylation of bifunctional coupling components of the general formula (V) in which the symbols q and r have the value 1. If, on the other hand, one starts from, for example, o-nitrobenzyl alcohol or o-nitrophenylacetic acid, then, after linking via the oxygen-containing radicals, hydrogenation and N-alkylation, bifunctional coupling components of the general formula (V) ₃ in which the symbols ^ q and r have the value 2. By coupling with a

Diazonium compound gives the corresponding dyes. Further suitable starting materials for the preparation of the bifunctional coupling components of the formula (V) are the anilines of the formula

wherein at least one, preferably both groups R, and Rp denotes the remainder of the formula -alkylene-Q, where Q is an acyloxy-, Is hydroxy, amino or cyano and d is the same Has meaning as above, but preferably a C-, ^ "alkyl

or -alkoxy group.

These anilines are attached to the free amino groups by means of reactive derivatives of organic difunctional acids, in particular of dicarboxylic acids connected.

B. diazo components;

Any diazotizing components can be used as diazo components bare heterocyclic amines which contain no acidic, water-solubilizing substituents, in particular but the amines that form a heterocyclic five-membered ring with 2 or 3 heteroatoms, especially one nitrogen and one or have two sulfur, oxygen or nitrogen atoms as heteroatoms, and aminobenzenes, in particular those of the formula

wherein a is a hydrogen or halogen atom, an alkyl or Alkoxy, nitro, cyano, carbalkoxy or alkyl sulfone group, b is a hydrogen or halogen atom, an alkyl, cyano or trifluoromethyl group and c 'is a nitro, cyano, carbalkoxy or alkylsulfonyl group.

From the series of heteroeyclic diazo components the following may be mentioned, for example;

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2-aminothiazole, 2-amino-5-nitrothiazole, 2-amino-5-methylsulfonyl-thiazole, 2-amino-5-cyanthiazol _J 2-Amino-4-methyl-5-nitrothiazole _i 2-Amino-4-methylthiazole _i 2-amino-4-phenylthiazole, 2-amino-4- (4'-chloro) -phenylthiazole, 2-amino-4- (4'-nitro) -phenylthiazole, 3r-aminopyridine , 3-aminoquinoline, 3-aminopyrazole, 3 -Amino-1-phenylpyrazolj 3-aminoindazole , 3-amino-l _i 2,4-triazole _J 5- (methyl-, ethyl-, phenyl- or benzyl) -1,2,4-triazole, 3-amino-l - (4'-methoxyphenyl) -pyrazole, 2-aminobenzothiazole, 2-Aπlino-6-methylbenzthiazole _J 2-amino-6-methoxybenzthiazole _i S-amino-o-chlorobenzothiazole, 2-amino-6-cyanobenzthlazole, 2-amino 6-thiocyanthiazole _J 2-amino-6-nitrobenzthiazole, 2-amino-6-carboethoxybenzthiazole, 2 ~ amino- (4- or 6) -methylsulfonylbenzthiazole,

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2-amino-1,3> 5-thiadiazole 2-amino-4-phenyl or ^ - 2-amino-5-phenyl-l .3 _{J J} 4 _{J-thiadiazole} 2-amino-3-nitro-5-methylsulfo -thiophene _J 2-amino-3j5-bis- (methylsulfo) -thiophene,

5-Amino-3-methyl-isothiazole _J Λ

2-aminO-4-gyano-pyrazole, 2- (4'-nitrophenyl) -3-amino-4-cyanopyrazole, 3- or 4-aminophthalimide. ■

Suitable aminobenzenes are, for example: aminobenzenes
l-amino-4-chlorobenzene, l-amino-4-bromobenzene, l-amino-4-methylbenzene,

l-amino-4-nitrobenzolj |

l-amino-4-cyanobenzene

l-Amino-2 _J 5-dicyanobenzene, l-Amino-4-methylsulfonylbenzene, l-Amino-4-carballcoxybenzene, l-Amino-2 _J 4-dichlorobenzene _J

l-amino-2 _J 4-dibromobenzene, - ■ -. ■■■

l-amino-2-methyl-4-chlorobenzene _ί l-amino-2-trifluoromethyl-4-chlorobenzene, l-amino-2-cyano-4-chlorobenzene , l-amino-2-carbomethoxy-4-chlorobenzene,

hoxy-4-cniorbenz (

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l-amino-2-carbomethoxy-4-nitrobenzene, l-amino-2-chloro-4-cyanobenzene _J l-amino - ^ - chlorine - ^ - nitrobenzene, l-amino-2-bromo-4 ~ nitrobenzene, l- ^{amino-2-chloro-i} l - carbätiioxybenzol, ^{l-amino-2-chloro-i} l - methylsulfonylbenzol, l-amino-S-methylsulfonyl - ^ - chlorobenzene, l-amino-2-methylsulfonyl-4-nitrobenzene, l-amino-2 _J 4-dinitrobenzene, l-amino-2 _J 4-dicyanobenzene _J l-amino-2-cyano-4-methylsulfonylbenzene, l-amino-2j o-dichloro - ^ - cyanobenzene, l-amino-2 _i 6-dichloro-4-nitrobenzene, l-amino-2,4-dicyano-6-chlorobenzene, 4-aminobenzoic acid cyclohexyl ester, l-amino-2 _i 4-dinitro-6-chlorobenzene and in particular l-amino-2-cyano -4-nitrobenzene; also l-aminobenzene-2-, -3- or -4-sulfonic acid amidej, such as N-methyl or Ν, Ν-dimethyl or diethyl amide.

C. Diazotization; and coupling:

The diazotization of the diazo components mentioned can be done according to methods known per se, e.g. with the help of mineral acid and sodium nitrite or e.g. with a solution of nitrosylsulfuric acid in concentrated sulfuric acid, take place,

10 9817/1971

The coupling can also be carried out in a manner known per se / e.g. in a neutral to acidic medium, if appropriate in the presence of sodium acetate or the like, the coupling rate influencing buffer substances or catalysts, such as dimethylformamide, pyridine, resp. its salts, are made.

The coupling is also advantageously carried out under «

Combination of the components in a mixing nozzle. This is understood to mean a device in which the liquids to be mixed are combined with one another in a relatively small space, with at least one liquid being passed through a nozzle, preferably under increased pressure. The mixing nozzle can, for example, be constructed and work according to the principle of the water jet pump, whereby the supply of one liquid in the mixing nozzle and the water supply in the water jet *

pump and the supply of the other liquid into the mixing nozzle of the connection in the vessel to be evacuated Water jet pump corresponds, this latter liquid supply also under increased pressure can be done.

However, others can also be used for rapid, possibly continuous • mixing in a small space suitable devices are used. .

After the coupling reaction has taken place, the formed non-quaternized dyes from the coupling

109817/1971

The mixture is easily separated off, for example by filtration as they are practically insoluble in water. If the dyes obtained are quaternized, they are salted out.

If the bifunktionellθ coupling component of the formula (V) with less than 2 mole coupled a diazonium compound of the formula DN = N anion, then a mixture which is a mixture of the novel disazo dyes having monoazo dyes, which falls also in the scope of the present invention.

II. Process variant b)

The new dyes are also obtained if, according to variant b), two monoazo dyes are attached to one another connected; for this purpose one can use dyes of the formulas

D _n —Ν = Ν — Α _Ί

¹ J ¹ ^ R ₁ via

(alkylene)

^X l

R VIb

D ₀ -N = NA ₀ IS / ⁴

² I ^{2 N} R ₂

(alkylene) _Ί

X ₂

respectively.

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-.25 -

^VIc

wherein X and X each contain a group containing at least one reactive atom, such as a carboxyl or sulfonic acid group or their acid halide groups, or a mobile halogen atom, or an acylatable group, such as above all an amino-mercapto or hydroxyl group, or their reactive derivatives, and R ₁ , R ₂ , R_, R ₁ ^, R ^, A ₁ , A ₂ , D ₁ , D ₃ , q and r have the same meaning as above, with the bifunctional compound Z. ¹ , which on condensation with the groups X and X _{p forms} the bridge member Z > condense to form the dyes of the formula (II) according to the invention, or | azo dyes of the formulas

D ₁ -N ^ NA ₁ - (alkylene) -jN

and VIIa or VIIb

/ ■

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² VIIc

, Α _χ , A _g , R ₁ , R ₃ , R, R ^, R ^, q and r die

have the same meaning as above and X, and X ₂ each denotes a group which is reactive towards addition-capable double bonds or oxirane rings and contains at least one active hydrogen atom, to a bifunctionally addition-capable compound of the formula Y, -Z-Yp, in which Y, and Y are each an addition-capable group Remainder of the formulas -CH = CH _p

or -CH z> ^G ^ o ^is add J, or

Azo dyes of the formulas Via, VIb and VIc, in which X ₁ and Xp each represent an SH group, oxidize to disazo dyes and optionally quaternize the disazo dyes obtained on at least one of the radicals D- or Dp if these contain quaternizable groups.

The link between two dyes that each have an acylatable or etherealizable group (e.g. OH:,. SH or Have amino group), is done according to methods known per se with the aid of bifunctional reaction components.

. These are mainly diesters, dihalides or anhydrides of organic acids, phosgene, diisocyanates,

109817/1971

Biscarbonic acid esters, etc .. The linkage of the two Starting monoazo dyes are thus done according to methods known per se, e.g. by amidation and / or Esterification, especially with azeotropic elimination of water, by transesterification with elimination of a volatile alcohol or phenol or by reaction with acid anhydrides, by reaction with dihalides of organic sulfon and carboxylic acids, the component present in the Az © tertiary amino group for the absorption of the released hydrogen halide can serve; In addition to the purely organic acid chlorides, the organophosphorus alkanephosphoric acid dichlorides, such as ethane or cyclohexane phosphonic acid dichloride can be used. Depending on the starting materials chosen, esters and / or amides are obtained or carbamic acid esters or ureas.

As examples of bifunctional, the ^ group 'Z -

Introductory reagents include the following:

A. Acid derivatives , such as the anhydrides, esters or especially the halides of the following acids:

Oxalic acid,

Succinic acid,

Malonic acid,

Adipic acid,

Sebacic acid,

Maleic acid,

Fumaric acid, 109 81 7/1 971

Diglycolic acid,

Methylene-bis-thioglycolic acid, 2,3-dibromosuccinic acid, thiodibutyric acid, tetrahydrophthalic acids, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, ■ phthalic acid,
Isophthalic acid,
Terephthalic acid, naphthalene-1,8- or -2,6-dicarboxylic acid, 2,5-thiophenedicarboxylic acid, puranedicarboxylic acid, sulfothiophenecarboxylic acid, sulfobenzoic acid, sulfoacetic acid, benzene or naphthalenedisulfonic acids, and also phosgene.

B. diisocyanates , especially aliphatic or cyclic diisocyanates, such as hexamethylene diisocyanate, cyclohexane-ln ^ -diisocyanate, and aromatic diisocyanates, such as toluene-2,4- or -2,6-diisocyanate or a mixture thereof, phenylene-1,4-diisocyanate, Diphenyl 4,4'-diisocyanate,

109817/1971

Diphenylmethane-4,4'-disocyanate,
Diphenylmethane 3i3 ^t -di.isocyanat,

Also diisocyanates of the naphthalene series, such as naphthylene-1,5-diisocyanate, or heterocyclic diisocyanates, e.g. benzofuran or urea and diisocyanates containing uretdione groups, such as 1,3-bis- (4'-methyl ^ V-isocyanato-phenyl) -uretdione, selenium mentioned as examples. The diisocyanates can optionally also be prepared in situ , for example by reacting bis-chloromethylbenzenes and sodium or lead cyanate in active solvents.

C. Epoxides , in particular alicyclic polyepoxides, in which at least one epoxy group is attached to the alicyclic ring, such as vinylcyclohexenedioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-e.poxycyclopentyl ether, ethylene glycol bis (3 _J 4-epoxytetrahydrodiene) -cyclo8-cyclopentadiene ether, (3i4-Epoxytetrahydrodicyclopentadien- "8-yl) -glycidylätheri Compounds with two epoxycyclohexyl radicals, which are connected via ester or acetal bonds, such as diethylene glycol bis (3,4-epoxyeyclohexanecarboxylate, 3succyno-ethyl) -6 roethyl ^ i ^ -epoxy-ö-methyl-cyclohexanecarboxylate and the acetal of 3,4-epoxyhexahydrobenzaldehyde and 3,4-epoxy. Cyclohexan-lil-dimethanOl, but especially bifunctional © compounds with two terminal epoxy groups, such as e.g. butadiene diepoxide, diglycidyl ether, dihydric alcohols,

109817/1971

such as glycol di-glycidyl ether, diglycidyl ether divalent Phenols, such as 4,4'-dihydroxydiphenylmethane, -dimethylmethane or -sulfone, diglycidyl ether from polyvalent Thiols, such as bis- (mercaptomethyl) -benzenes, the Ν, Ν'-diglycidyl compounds, e.g. from N, N'-dimethyl-4,4'-diaminodiphenylmethane, Ethylene urea or oxamide, and diglycidyl esters of aliphatic, cycloaliphatic or aromatic dicarboxylic acids, such as phthalic acid, hexahydrophthalic acid, Tetrahydrophthalic acid or succinic acid, di- or triglycidyl cyanurate or isocyanurate.

All linking reactions are carried out according to methods known per se in aqueous and / or organic Solvents, optionally carried out in the presence of acid-binding agents; so you can do the reaction with diisocyanates either in inert solvents or

* without solvents at moderate temperatures, but also perform in active solvents.

Phosgene can be used directly, if necessary in stages, i.e. initially with the production of the chloroformic acid ester of one azo dye, are implemented. One can, however, also use bis-carbonic acid diester or -diamide - (= bis- ' Urea) bridges or bis-carbamic acid ester bridges or Corabinations of such bridges can be obtained by adding, for example, 2 moles of the CMoroformic acid ester of an azo dye with one mole of a diol, a diamine or a dithiol zum.IHurethan, Bis- (thioursthan) or bis-urea-

109817/1971

connection implemented.

As such divalent aliphatic cycloaliphatic, Araliphatic or aromatic hydroxyl, mercapto or amino compounds may be mentioned: 1,2-dihydroxyethane, 1,2- or 1,3-dihydropropane, .1,2- or

1,3- or 1,4- or 2,3-dihydroxybutane, 1,2- or 1,3- or

1,4- or 1,5- or 2,3- or 2,4-dihydroxypentane, the corresponding dihydroxyhexanes, -heptanes, -octanes, -nonanes, -decanes, -undecanes, -dodecanes, -hexadecanes, -octadecanes, 1,4 Dihydroxybutene, 1,4-dihydroxy-2-methylbutane, 1,5-dihydroxy-2,2-dimethylpentane, 1,5-dihydroxy-2,2,4-trimethylpentane, di- (β-hydroxyethyl) thioether , Di- (ß-hydroxyethyl) ether (= diglycol), triglycol, cyclohexanediol-1,2 or -1,3 or -1,4, 4,4 ^! -Dihydroxydicyclohexylmethane, ^^ '- dihydroxy-dicyclohexylmethylmethane, 4,4' -dihydroxydicyclohexyldimethylmethane, 4-hydroxybenzyl alcohol,

1,4-di- (ß-hydroxy-ethoxy) -benzene, 1,2- or 1,3- or j

1,4-dihydroxybenzene, 1-methyl-2,4- (or -2,3- or -3,4- or - ^, 6- or -2,5- or -3,5) -dihydroxybenzene, 1 , 3-dimethyl-2,4- (or -4,6) -dihydroxybenzene, 1,4-dimethyl-2,5-dihydroxybenzene, l-ethyl-2,4-dihydrΌxybenzene, l-isopropyl-2,4- dihydroxybenzene, 2,4- or 4 _J 4 ^t -DihydroxydiphenylMther, 2,2'-Dihydroxyäthylenglykoldiphenylather, 1,3- or 1,4- or 1,5- or 1,6- or 1,7- or 1,8 - or 2,6- or 2,7-dihydroxynaphthalene, 4,4'-dihydroxydiphenylamine, 2,4'- or 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl

1098 17/197 1

methane, 4,4'-dihydroxydiphenylmethyl methane, 4,4'-dihydroxydiphenyldimethyl methane, 1,1'-di (4'-hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenyl (di) sulfide, 4,4'-dihydroxydiphenyl sulfone or corresponding aliphatic and aromatic dithiols.

1,2-diaminoethane, 1,2- or 1,3-diaminopropane, 1,2- or 1,3- or 1,4- or 2,3-diaminobutane, 1,2- or

^ 1,3 ~ or 1,4- or 1,5- or 2,3- or 2,4-diaminopentane, the corresponding diaminohexanes, -heptanes, -octanes, -nonanes, -decane, -undecane, -dodecane, -hexadecane, -octadecane, 1,4-diaminobutene, 1,4-diamino-2-methylbutane, 1,5-diamino-2,2-dimethylpentane, l, 5-Dlamino-2,2,4-trimethylpentane, di- (ß-aminoethyl) -thioether, di- (γ-aminopropyl) -ether, Di- (7 ~ aminopropyl ether - (/ ü, i / 0-diamine, di- (U) -aminohexyl) -thioether, NjN-dimethyldiaminoethane-l ^, N, N -'- diethyldiaminoethane-1,2, l-amino-3-methylaminopropane, isophoronediamine,

fc piperazine, · N-2-aminoethyl-piperazine, 4-aminopiperidine, 1A), W-diamino-1,3 (ode-r -1,4) -dimethylbenzene, (λ) , W-diamino-1,4 - (or -l, 2) -dimethylcyclohexane, W, (x) -diamino-1,4-diethylbenzene, ω, W-diamino-1,4- (or -1,5) -dimethylnaphthalene, ω, ω-diamino -di-n-propylbiphenyl, 1,2- or 1,3- or 1,4-diminocyclohexane, l-methyl-2,4-diaminocyclohexane, l-ethyl-2,4-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylmethyl methane, 4,4'-diaminodicyclohexyldimethyl methane, 4,4'-diamino-2,2'-dimethyldicyclohexyl methane., 4,4'-diamino-3, 3 '-dimethyldicyclohexyl-

109817/1971

methane, 4-aminob.enzyl.amine, ■ 2- (4- ^| - aminophenyl) -l-amiho-. ethane, l- (3 ^{L-aminophenyl)} -l-aminoäthan, 3- (3'- or 4V-aminophenyl) -l-aminQpropan, J5 (3 'or 4 ^T -AminQphenyl) -1-aminobutane, TetraJiydronaphthylendiarnin- 1,5 or -1,4, Hexahydrobenzidin-4,4-diamine ^I, Hexahydrodlphenylmethan-4,4'-diamine, 1,2-, 1,3-, 1,4-diaminobenzene, 1-methyl-2,4 - (or -2,3- or -3,4- or -2,6- or -2,5- or -3,5) -diaminobenzene, 1,3-dimethyl-2,4- (or - 4.6) - m

diaminobenzene, 1,4-dimethyl-2,5-diaminobenzene, 1-ethyl-2,4-diaminobenzene, l-isopropyl-2,4-diaminobenzene, diaminodiethylbenzene, Diisopropyl-diaminobenzene, l-chloro-2,4-diaminobenzene, l, 3-dichloro'-2,4- (or. -4,6) -diaminobenzene, 1,4-di-chloro-2,5-diaminobenzene, 2,4- (or 4,4 ') -diaminodiphenyl ether, Ethylene glycol diphenyl ether-2,2'-diamine, Diethylene glycol diphenyl ether-2,2'-diamine, N, N'-dimethylpixenylenediane] in-1,3 or -1,4, N-methylphenylenediamine-1,4;

. 1,3- or 1,4- or 1,5- or 1,6- or 1,7- or \

1,8- or 2,6- or 2,7-naphthylenediamine,!, L'-dinaphthyl-2,2 ^I- diamine, 4,4'-diaminodiphenylarain, 2,4'- or 4,4'-diaminodiphenyl, 3,3'-dimethyl-4,4 ^f -diaminodiphenyl,. 2,2'- or 3,3 '~ dichloro-4,4'-diaminodiphenyl, 4i4'-diaminodiphenylmethane, 4,4-diaminodiphenylmethane ^f, 4,4'-diphenyldimethylmethane-DiEmInO, 2,2'-dimethyl-4, 4'-rdiaminodiphenylmethan, 2,5,2 ', 5'-tetramethyl-4,4'-dlaminodiphenylmethan, l, l-di- (4'-aminophenyl) cyclohexane, l _i l-di- (4 -amino ^f -3'-methylphenyl) -cyclohexane, 3ί3'-dlaminobenzophenone,

109817/1871

- 2,4-diaminodiphenylethane-1,2,4 ', 4 "-triamihotriphenylmethane, 4,4'-diamino-2,2', 5 * 5'-tetramethyltriphenylmethane, 4,4'-diamino-2,2 ', 5 _i 5 ^l -tetramethyl-2 "-chlorotriphenylmethane, fluorenediamine-2,7- or -2,6-diaminoanthraquinone, 9-ethylcarbazole-3,6-diamine, pyrene-3 # 8-diamine, chrysene-2, 8-diamine, benzidine-4,4'-diamine, diphenylsulfide-2,4'-diamine, diphenyl disulfide-4,4'-diamine, diphenylsulfone-4,4'-diamine,

■ t Diphenylmethanesulfon-4,4'-diamine, 4-methyl-3-aminobenzenesulfonic acid (4'-aminophenyl) ester, Di- (4-aminobenzenesulfonyl) -äthylenediamine-3i 3 '"• dimethoxy-4,4'-diaminodlbenzylthioether, 4,4'-dimethoxy-313'-diaminobenzothioethylene glycol and 3> 3'-dimethoxy-4,4'-diaminodlbenzyl sulfone.

In addition to dialcohols, dithiols and diamines, bifunctional compounds can of course also be used two different of the punctures mentioned exhibit.

|| The introduction of ether bridges takes place e.g.

by reacting alkali phenolates with dichlorides such as 1,4-dichlorobutene, di-ß-chloroethyl ether, dichloroethyl formal and isomers of bis (chloromethyl) benzene, or by additive reaction with bifunctional parts Compounds that have additive double bonds (such as divinyl sulfone), or rings capable of addition, such as dihy, dropyranyl rings (see 2.B. British Patent No. 996 705) or in particular epoxy rings.

109817/1871 "

"■ · - 35 - V. '.; ■

The dyes of the formulas Vila, VIIb and VIIc are reacted with these last-mentioned compounds; as such, the monoazo dyes described in Belgian patents 685 628, 685 765, 685 766 and 685 768 can also be used, which correspond to the formula VIIc, the group of the formula -R ₂ V-Xp representing a β- (vinyl sulfone) - ethyl group.

If the two dye radicals of the formula VIIa and VIIb or VIIc, in which the reactive groups X- and X- each represent a primary or monoalkylated amino group, are reacted with a diepoxide of the formula CH-) _O Z ', one according to the invention is obtained

■■■■. Disazo dyes of the formula II, wherein Z is the remainder of the

Formula -R ¹ N-CH ₂ -CH-Z-CH-CH ₂ -NR ¹ -, in which R '

; OH OH

is hydrogen or alkyl.

The conversion of amino groups on the aromatic nucleus forms one of the basic reactions epoxy resin chemistry and has therefore been studied in every respect, e.g. in the works of Lee and Neville, "Epoxy Resins" New York, 1957, and Houben-Weyl, "Methods of Organic Chemistry", Volume 14, Part 2, Stuttgart 1963, pp.462-567, are dealt with in detail, just like there the reaction with other functional parts Groups and the usual diepoxides of epoxy resin technology are described.

109817/1971

The quaternization can according to the invention are carried out on the new disazo dyes of the formula (II) if at least one of the two radicals D, and Dp is quaternizable, where if χ = 1, q = 1 and r = 1 and the radicals D, and D_ are each a heterocyclic System and Z represent two "oxygen atoms" which are directly different from the aromatic radicals A and A or two carbon ™ connected via the nitrogen atom acid amide groups, the bridge member Z at the same time either an unsaturated, aromatic or heterocyclic one Contains radical or a carbon chain interrupted by at least one heteroatom. One goes in the Usually from finished disazo dyes, which for this purpose with esters of strong mineral acids or organic sulfonic acids, such as dimethyl sulfate, alkyl or aralky! halides, such as methyl bromide or benzyl chloride, methanesulphonic acid methyl ester, or optionally substituted esters Benzenesulfonic acids, such as ethyl 4-methyl-, 4-chloro- or 4-nitrobenzenesulfonic acid be treated. The alkylation is preferably carried out by heating in indifferents organic solvents, for example xylene, carbon tetrachloride, o-dichlorobenzene and nitrobenzene. However, solvents such as acetic anhydride, dimethylformamide, acetonitrile or dimethyl sulfoxide can also be used. be used. The quaternized dyes preferably contain the remainder of a strong anion as the anion

109817/1971

Acid, such as sulfuric acid or its half-ester, or a halide ion, but they can also be used as double salts, for example with zinc chloride, or as free bases.

The invention also relates to the bifunctional coupling components of the general formula

H I

- (alkylene) - ^ - Z—

x-1 -H

wherein Äp A ₂ , R ₁ , R ₂ , Ry R ₁ ^, H ^, x _s r, q and Z have the same meaning as in iorüil il; itiän -i it by condensation of a combination of formulas

2-x

rtiit a fading of the Föraiei

ι ■■■

or with a connection of the Förhiei

1D9817 / 1

Ε «Η— A ₀ V

where the symbols A ,, A ₀ , R ₁ , R ₀ , R ^, Rj ,, Ri, X ₁ and X _{0 have} the same meaning as in the formulas Via, VIb and VIc.

Preferred among these are the diamines of the formula

t?

R ₁ R, N — JL-MAlkylen) - _T -Z—

wherein R ₁ , R, R, and R ^ , A ₁ , A ₃ , Z, q and 4 * have the same meaning as in the formula IV.) i These diamines are obtained if one receives the above

1 V

The timing described under (b) or (c) with the bi-functional connection of the Forätel Z * is carried out, but instead of a dye component, the corresponding coupling components of the Förnieih are used

r ^ ünä I ^ {»äm ^ 0j ^ 2K

109811/1971

used, wherein R ,, R ₀ , R-, R,., Ri !, A ₁ , A ₀ , q and r

have the same meaning as above and X and Xp each have a group containing at least one reactive hydrogen atom, such as a carboxyl ode.r sulfo group, preferably an acylatable group, such as above all an amino, mercapto or hydroxyl group, or their reactive derivatives , or a reactive halogen atom. '' ■ ■ 'Λ Appropriately, one goes from the appropriate

Nitro compounds of the formulas

H H

.— (alkylene) ₁ -UiO ₀ and - .. X ₀ - (alkylene) ₀ -NO ₀

L Q. ~ -L X. c. c. x-J. cc

from where R ,, R _? , R-, Rk, A-., Ap, q, r, X ₁ and Xp have the same meaning as above, and sets the nitro compounds in the manner described above with the bifunctional compound of the formula Z ^T to the bisnitro | compounds of the formula

O ₀ NA ₁ (alkylene) - ^ rZ - (alkylene) - r - A ₀ -NO ₀

c. ι J_ Q ~ J- x. ~ J- \ cc

I I

H H

The bisnitro compounds are then reduced to the bisamino compounds, with one after known methods. Both catalytic reduction with hydrogen in the presence of is suitable

109817/1971

Raney metals, such as Raney nickel, or noble metal catalysts, such as platinum and palladium catalysts, as well as reduction with reducing agents such as tin or iron, in the presence of acid. The free bisamino compounds obtained are then optionally alkylated on the amino groups, whereby one as alkylating agents, alkyl halides, such as ethyl chloride, monoepoxides, such as ethylene oxide, halohydrins, such as ethylene chlorohydrin, or can use ethyleneimine. The alkyl groups on the nitrogen atom are optionally used further implemented by, for example, ß-hydroxy or ß-aminoethyl groups acylated with acid chlorides, anhydrides or isocyanates.

III. Use.

The dyes described above, their mixtures with one another and their mixtures with other azo dyes are excellent, especially after being converted into a finely divided form, e.g. by Grinding, pasting, falling over, etc., for dyeing and printing of synthetic fibers, such as acrylic or acrylonitrile fibers, polyacrylonitrile fibers and mixed polymers from acrylonitrile and other vinyl compounds, such as acrylic esters, acrylamides, vinyl pyridine, vinyl chloride or Vinylidene chloride, copolymers of dicyanethylene and vinyl acetate, as well as from acrylonitrile block copolymers, fibers made from polyurethanes, cellulose tri- and 2 1/2 acetate, polyamides,

109817/1971

such as nylon 6, nylon 6.6 or nylon 12, and in particular Aromatic polyester fibers such as terephthalic acid and ethylene glycol or 1,4-pimethylolcyelohexane, and copolymers of terephthalic and isophthalic acid and ethylene glycol.

-.- ■■■■ The present invention is therefore

also a method of dyeing or printing synthetic Fibers, especially polyester fibers, which thereby is characterized in that one of carboxyl and sulfo groups free, water-insoluble disazo dyes in which the residues of the formula I by a divalent bridge Z without dye character are connected, but especially those of the formula ΙΓ, their mixtures with one another and their mixtures with other azo dyes used.

The dyeing process, especially for ester group

containing fibers, is preferably used with such dyes carried out, which in the colorless Broken member Z the diacyl "rest a divalent organic acid, especially one Dicarboxylic acid.

Furthermore, fibers containing ester groups are advantageously dyed with dyes of the formula III in which at least the radicals R ₁ and R 2, preferably also the radicals R, and R ₂ , represent a β-acyloxy, β-cyano or β-hydroxyethyl group , the acyl radical being the radical of an organic acid.

If the above new dyes the

Formula (II) one or two quaternized diazo radicals of the formula

BJe mel D, and / or D ₂ contain, / are particularly suitable for the dyeing of fibers and fabrics of the polyacrylic type. here

1 0 9 8 1 7/1971

the dyes occupy a preferred place, those of the Formula (III) correspond.

Among the dyes of the formula IV, preference is given to choosing those in which q and r both have the value 2 to have.

For dyeing, the water-insoluble, non-quaternized dyes are advantageously used in finely divided form

~ Shape and color with the addition of dispersants, such as P.

Sulphite cellulose waste liquor or synthetic detergents, or

a combination of different wetting and dispersing agents. As a rule, it is expedient to convert the dyes to be used into a dye preparation before dyeing Contains dispersant and finely divided dye in such a form that when diluting the dye preparations with water a fine dispersion is created. Such dye preparations can be prepared in a known manner, for example by grinding the b Dye in dry or wet form with or without additives of dispersants in the grinding process. Man can also dye the above synthetic fibers in organic solvents that contain the dye in dissolved form.

In order to achieve strong colorations in polyethylene terephthalate fibers, it is expedient to add a swelling agent to the dye bath, or to carry out the dyeing under pressure at temperatures above 100 ° C, for example at 120 ⁰ C. Aromatic carboxylic acids, for example benzoic acid or salicylic acid, are suitable as swelling agents,

10 9 817/1971

Phenols / Vie for example ο- or p-oxydiphenyl, salicylic acid methyl ester, aromatic halogen compounds such as chlorobenzene, o-dichlorobenzene or trichloro; benzene / phenylmethylcarbinol or diphenyl. At oen Dyeing under pressure proves to be advantageous that To make the dyebath slightly acidic, for example by adding a weak acid, e.g. acetic acid.

The non-A to be used according to the invention

Quaternized, water-insoluble dyes turn out to be as particularly suitable for dyeing according to the so-called heat setting process, after which the fabric to be dyed with an aqueous Dispersion of the dye, which is expediently 1 to 50 $ Contains urea and a thickening agent, especially sodium alginate, preferably at temperatures of at most 60 ° C and squeezed off as usual. Appropriate it is squeezed in such a way that the impregnated product retains 50 to 100 $ of its initial weight in dyeing liquid. | This is how it is used to fix the dye

impregnated fabric, practical by prior drying, for example in a stream of warm air at temperatures of about 100 ⁰ C, for example between l80 to 21Ö ° C, heated.

That which has just been mentioned is of particular interest Thermosetting process for dyeing blended fabrics made from polyester fibers and cellulose fibers, in particular cotton. In this case, the padding liquid contains in addition to that according to the invention to be used non-quaternized

10981 771971

_ 44 -

water-insoluble dye or dyes suitable for dyeing cotton, for example direct dyes or Vat dyes, or especially so-called reactive dyes, i.e. dyes which can be fixed on the cellulose fiber with the formation of a chemical bond, for example Dyes containing a chlorotriazine or chlordiazine radical. In the latter case, it proves to be expedient to use the Padding solution an acid-binding agent, for example an alkali carbonate or alkali phosphate, alkali borate or add perborate or mixtures thereof. When using vat dyes a treatment of the padded Fabric after heat treatment with an aqueous alkaline solution of a common in vat dyeing Reducing agent necessary.

According to the present process on polyester fibers The dyeings obtained are expediently subjected to an aftertreatment, for example by heating with an aqueous solution of an ion-free detergent.

Instead of by impregnation, the specified dyes can also be used according to the present process can be applied by printing. For this purpose, one uses, for example, a printing ink that is next to that in the printing house customary auxiliaries, such as wetting agents and thickeners ^ the finely dispersed dye, optionally in a mixture with one of the above-mentioned cotton dyes, optionally in the presence of urea and / or an acid-binding one

109817/1971

Means, contains.

According to the present catch, rnan

strong dyeings and prints with excellent fastness properties, especially good light, sublimation, decatur, washing and fastnesses to chlorinated water. The dyeings on acetate silk are also characterized by good gas fastness. Another advantage is the good wall and cotton reserves the dyes to be used according to the method.

One can use the new water-insoluble, non-quaternized Also use dyes for spin dyeing polyamides, polyesters and polyolefins. That too Coloring polymers are expediently in the form of powder, grains or chips, as a finished spinning solution or in the molten state mixed with the dye, which in the dry state or in the form, a dispersion or Solution is introduced in an optionally volatile solvent. After homogeneous distribution of the dye In the solution or melt of the polymer, the mixture is in a known manner by glessening, pressing or extruding ζμ fibers * yarns, mqno threads, films etc. processed.

The new water-soluble quaijemized dyes or dye salts are suitable for dyeing and printing on a wide variety of fully synthetic fibers, such as polyvinyl chloride, polyamide, polyurethane and especially polyacrylic fibers, dyes of the formula (I ¥), which are in the diazo radicals D and D ₂ One quaternized each

109817/1971

have aliphatic amino groups, pull on untannic cotton.

The new dyes are also suitable for the mass coloring of polymerization products of Acrylonitrile, from polyolefins * as well as other plastic ones Masses, also for the coloring of Qelffarben and lacquers, The above-mentioned Thermafixierverfahren ™ can also be used.

Some of the new water-insoluble, non-quaternized dyes are also valuable pigments, many can be used for a wide variety of pigment applications, e.g. in finely divided form for dyeing rayon and viscose or cellulose ethers and esters, for the production of inks, especially ballpoint inks, as well as for the production of colored lacquers or lacquer formers, solutions and products made of acetyl cellulose, nitrocellulose , natural resins or synthetic resins, such as polymerization resins or condensation resins, e.g. aminoplasts, alkyd resins, phenoplasts, polyolefins, such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, rubber, Casein, silicone and silicone resins.

In the following examples, unless otherwise stated, the parts mean parts by weight, the percentages by weight and the temperatures are given in degrees Celsius.

109817/1971

Production of the bifunctional coupling components.

Regulation IA. "

Production of the bis-nitro compound.

To a mixture of 55 * 6 parts of 3-nitrophenol, idO parts of ethyl alcohol and 22.4 parts of caustic potash with stirring at 80 to 83 ° 35 / MIe: ethylene bromide added dropwise the mixture is then stirred under reflux for 15 hours and cooled and filtered. The residue is washed first with warm water, then with a little cold ethyl alcohol, then pressed and dried at 60 to 70 °. 29 g are obtained of the product of the formula

Pp. 139.5 to 14E, 5 °.

Analysis: C calc. 55 * 2 ^ C found. 55,

H calc. K, 0% H found. 3,

N calc. 9.2 $ N found. 9.,

109817/1971

Regulation IB. Production of the bis-amine.

6.08 parts of the product prepared above are in 250 parts of absolute ethyl alcohol with a catalyst of Hydrogenated palladium on charcoal; the hydrogen uptake

is 2.7 1 ($ 100 of theory). After finished mercury recording . is heated to the boil with a little animal charcoal and filtered hot through kieselguhr P. 3.2 parts crystallize from the piltrate of the diamine of the formula

Γ ² F ²

U-0- (CH _{9) 0} - 0-U

in fine white needles; Pp. 1J54 to

109817/1971

Regulation IIA. Preparation of the bis-nitro compound.

To a solution of 13.8 parts of m-nitroaniline in 160 parts of pyridine become 9.15 parts of adipic acid dichloride at 15 to 20 ° added dropwise and stirred for 2 hours at room temperature. The resulting precipitate is pressed out with Water / $ 10 soda solution and alcohol washed, in vacuum tube tank dried at 60 °. There remain 12.1 parts of the product formula

H H.

V- fGH)

NO ₀ II ^d

Pp. 240 to 245 °.

109817/197 1

Regulation IIP. Production of the bis-amine.

The HA produced according to Procedure bis-nitro compound _S as hydrogenated in the provision IB to give the diamine of the formula

H H

0 0

65 parts of the amine thus obtained are heated together with 150 parts of acrylonitrile and 12 parts of glacial acetic acid in the autoclave to 135 to I ² K) ⁰ C and stirred for 15 hours at this temperature. After emptying the autoclave, the solution is concentrated in a vacuum, and the precipitate after some time abfil- W trated and triturated with a little ether. After drying, a product of the formula is obtained

₂ HN

^S NH — C0- (CH ₂ ) —CO — NH ^/

1098 17/197 1

In an analogous way one obtains the connections of the formulas:

HC ₀ H, -CN
V "2 4

H C ^ H. \ / 2 4

CH-CH

C-CO-]

_J 2

109817/1971

HC ₀ H.-CN N

CH ^ O

-NH-CO-CH

HC ₀ H ₇₁ -CN
N

CH ₃ O

'NH-CO-CH,

NH,

CH O

'NH-CO-CH,

NH-CO-CH,

10 9 8 17/1971

Regulation IIIA.

N-bis-ß-acetoxyaethyl-3-nitro-aniline.

1 mol of N-bis-ß-hydroxyethyl-3-nitroaniline (obtainable in accordance with Swiss patent specification 171,721) is heated to 130 ° C. for 3 hours together with 2.2 mol of acetic anhydride, then the glacial acetic acid is removed in vacuo and the residue is distilled in a high vacuum. N-bis-ß-acetoxyethyl-3-nitro-ariline is obtained, which has the following analytical composition. ;

Calculated: C 5 ^, $ 19 H 5.85 ^ N $ 9.03 - found: C 5 ^ 25 ^ H 5.78 ^ N 9

N-bis-ß-acetoxyethyl-3-amino-aniline.

2 MoT N-bis-ß-acetoxyethyl-3-nitro-aniline are in

2 liters of absolute ethanol hydrogenated with the addition of Pd / charcoal; ä then the solvent is removed in vacuo and the residue is distilled under high vacuum. N-bis-ßacetoxyethyl-3-amino-aniline is obtained.

109817/1971

171S381

Regulation IIIB. Production of the bifunctional coupling component.

l / lO moles of N-bis-.beta.-acetoxyethyl - ^ - amino-aniline are dissolved together with 40 g of pyridine in 9 S chlorobenzene and thiophene-2,5-dicarboxylic acid chloride are added batchwise at 70 to 75 ⁰ C with 1/20 Mol. Allow to stir overnight, remove the solvent in vacuo and recrystallize the residue, which solidifies after a while, from methanol. The bis-amine of the formula is obtained

CH "C00H, G ₀ / ^N C _O H, 0C0CH" 342 243

N30-J | ~ P-C (/

CH-COOH. 3 4

^N C _O H.0C0CH "24 3

1 0981 7/1971

U6i 7

( ² HD) -HM-OO-HM

² HO-OO-O-Vd

- ² HO-OD-HM

^ HD-OD-HM

² HD-OD-O-Vd

: ueiti

Regulation IV

A. Production of Ν, Ν-bis (ß-cyanoethyl) -3-acetylamino -aniline. _:

150 parts of 3-amino-acetanilide (manufactured by Acetylation of 3-nitro-aniline and subsequent reduction) together with 9 parts of copper (I) chloride, 65 parts of glacial acetic acid and 150 parts of acrylonitrile in the autoclave heated to 120 ° C. for 20 hours. After cooling, P becomes the mixture along with dilute hydrochloric acid for some time stirred. The precipitate is filtered off, well with water washed and dried in vacuo. After recrystallization from ethyl acetate, a product of the formula is obtained

₀ C H-CN

OH ' ⁴

IN) ₉ H-CN

NH-CO-CH ^{ά 4}

B. Preparation of 3-amino-N, N-bis (ß-cyanoethyl) aniline. w 10 parts of N, N-bis-ß-cyanoethyl-3-acetylamino-aniline

are in 100 parts by volume of ethanol with the addition of conc. Hydrochloric acid stirred under reflux for 3 hours. Immediately afterwards, the solvent is removed on a rotary evaporator, the residue taken up in cold water and the solution was quenched by addition of lO ^ soda solution to a pH value between 6 provided to J. The first oeligi precipitate solidifies after a while, then filtered off, washed well with water and dried in vacuo.

t 0 9 817/1 9 7 1

A product of the formula is obtained

C ₂ H-CN

The IR spectrum clearly shows that the cyano groups not saponified, but the acetyl group was completely split off.

Analogous to regulation III one obtains from it by reaction with

or isocyanates

Dicarbonsäureehloridery the compounds of the formulas:

C ^ H.-CN 2 4

NH-

CH-CH -CO-C Ä-CO-

C _O H, -CN

NH-CO-CH

10 9 8 17/1971

IiH-CO-CH ₂ -CH ₂

-cn

NH-CONH- (CH ₂ ) -

Regulation V. A. Preparation of the bis-nitro compound.

37j6 parts of 3-nitro-phenyl isocyanate are suspended in 100 parts of chlorobenzene VoIi-, J, l parts of ethylene glycol were added dropwise, and further 20 parts by volume of chlorobenzene added. The mixture is then heated to 70 ^° C., stirred at this temperature overnight and then the reaction mixture is cooled. The precipitate is filtered off, washed with a little cold ethanol and dried in vacuo. A product of the formula is obtained

109817/1971

B. Preparation of the bis-amine.

33 parts of the bisnitro compound obtained are in 200 parts by volume of dimethylformamide hydrogenated with the addition of 10 # palladium-carbon as a catalyst. After filtering off of the catalyst, the solution slowly becomes an excess Ice water is added. The resulting precipitate is filtered off, washed with water and dried in vacuo. You get a product of the formula

In an analogous way one obtains:

10 9 8 1 7/1971

NH

^ NH-CO-NH- (CH ₀ ) .- NH-C0-NH ^/

c. D.

NH

NH,

NH

NH-CO-Nh-CH ₂ -CH-NH-CO-NH

HC _O H.-CN V 2 4

HC ₀ H.-CN ν 2 4

10 9 817/1971

Regulation VI. A. Preparation of the bis-nitro compound.

a) 2>, 7 parts of o-nitro-chlorobenzene, 4.6 parts of ethylene glycol and 150 parts by volume of dimethylsulfoxide are heated with stirring to 70 ⁰ C. At a temperature between 70 and 80 ° C., 50 $ strength sodium hydroxide solution is added dropwise, then the reaction mixture is heated to 85 to 90 ° C. and stirred at this temperature overnight. The mixture is then poured onto ice, stirred for some time and the precipitate is filtered off. Finally the residue is washed well with water and dried in vacuo.

b) 35.4 parts of 2-nitrophenol potassium are suspended in 75 parts by volume of ethanol and heated to 7O ⁰ C. At this temperature, 18.8 parts of ethylene bromide are added dropwise and the mixture is stirred under reflux overnight. After cooling, the precipitate is filtered off, washed well with water then with a little cold ethanol and dried in vacuo. A product of the formula is obtained by both processes

N02

109817/1971

- 62 B. Production of bis-amine.

11 parts of the resulting Bls-nitro compound are in 120 parts of dioxane with the addition of Raney nickel as a catalyst hydrogenated. After filtering off the catalyst and removing the solvent in vacuo, a product of the formula is obtained

In an analogous way one obtains:

P- (CH ₂ )

NH ₀ NH

ι ₂

NH.

° 6 ^H 11

(CHJ ₀ -OA

109817/1971

NH-C ₀ H.-CN ι 2 4

AO-CH ₂ -CH ₂

109817/1971

Regulation VII.

9.5 parts of N-β-cyanoethyl-N-β-oxyethyl-aniline are dissolved in 25 parts by volume of chlorobenzene and 8.2 parts of 3-nitro-phenyl isocyanate are slowly added. After adding more vol. Chlorobenzene is slowly heated to 7O ⁰ C and stirred overnight at this temperature. After cooling, the solvent is removed on a rotary evaporator and the residue, which solidifies after prolonged standing, is triturated with ether. After filtering off, the residue is dried in vacuo. A product of the formula is obtained

-W - I.

Xf _O H -O-CO-NH- <CZ>

2 4

53 parts of the product obtained are in 5OOV0I.-T. Dimethylformamide with the addition of palladium-carbon 10 $ ig as Hydrogenated catalyst. After filtering off the catalyst and removing the solvent, a product is obtained the formula

Y ^{2 4}

^X C HO-CO-NH-10 9 8 17/1971

When using 2-nitro-phenyl isocyanate instead of 3-Nitro-phenyl isocyanate, the bifunctional coupling component of the formula is obtained

<Z>< ²⁴

In an analogous manner, by reacting the above-described N-bis-ß-acetoxyethyl-3-amino-aniline with 2- or 3-nitro- ■ phenylisoGyanate and subsequent hydrogenation the bifunctional Coupling components of the formulas

CLEL-O-OO-CH-

109817/1971

Starting from N-ß-hydroxyethyl-N-ethylaniline and The coupling component is obtained from 3-nitro-phenyliso.c.yanat the formula

NH- <m>

J ₀ H, -0-C (H.

The addition of 1 mol of acrylonitrile gives the coupling component of the formula

ί -0-CO-NH-

109817/1971

Regulation VIII.

A. Preparation of the Bls-nitro compound. .

33.6 parts of 4-amino-2-nitro-anisole are in 100. VoI. Sharing Chlorobenzene suspended and slowly 32 * 8 parts 3-nitro-phenyl isocyanate added. After adding more 200 parts by volume of chlorobenzene is the mixture to 70 to 75 ° C heated and stirred at this temperature overnight. After cooling, the precipitate is filtered off and washed with washed some ethanol. After the precipitate has been dried in vacuo, a product of the formula is obtained

B. Production of bis-amine.

56 parts of 3 * 3'-dinitro-4-methoxy-dipheny! Urea in 200 parts by volume of dimethylformamide with the addition of Raney f Hydrogenated nickel as a catalyst. After the catalyst has been filtered off, the solution is added to an excess with stirring Ice water, filter off the precipitate and wash it well with water. After drying the precipitate in a vacuum one obtains a product of the formula

^CH 3 ° ^ L_> ~ NH-CO-NH- <Z ~>

1098 17/1971

In an analogous manner, one obtains by reacting m-nitroaniline and m-nitrophenyl isocyanate and then reducing it the product of the formula

NH ₀

When using the corresponding p-Methoxyderlvate obtained one the coupling component of the formula

- <Z> -OCH ₃

. Regulation IX.

A. Representation of the chlorocarbonic acid ester of N-ß-hydroxy ethyl-N-ß-cyanoethyl-aniline.

™ 100 parts by volume of chlorobenzene are at 0 to 10 ⁰ C with

Phosgene saturated. 19 parts of N-ß-cyanoethyl-N-ß-oxyethyl-aniline are then added in 50 parts by volume at the same temperature Chlorobenzene too. After adding a further 50 parts by volume of chlorobenzene, phosgene is added to the mixture Warm up to room temperature, then heated to 50 C for 2 hours and then to 80 to 85 C. At this temperature phosgene is passed in with stirring until a clear solution is formed. Then stir for a few hours at the

109817/1971

-.69 -

the same temperature and blows the excess phosgene with nitrogen. The hot solution is filtered with exclusion of moisture, the solvent is removed in vacuo, the residue, which solidifies after a while, triturated well with chloroform and dried in vacuo. You get a product of the formula

^ ₂ H ₄ -C-CQ-Cl ■ '; ./ ■: ■

that is protected from moisture until further use must become.

According to the IR spectrum, the compound is in solid form as an amide; in the reaction described below, however, the product behaves as a carbonic acid ester.

B. -Production of the bifunctional coupling component.

14 parts of N-bis-ß-acetoxyethyl - ^ - arolno-aniline are dissolved in parts by volume of toluene and 4.5 parts by volume of pyridine. At a temperature of 20 to 3Q ⁰ C is added slowly 12.7 parts ■ Chlorkohlensäureester of N ~ ß-cyanoethyl-N-.beta.-oxyäthy! Aniline are added and stirred after addition of 25 ¹ IOI ^ ToIUoI overnight at room temperature. The mixture is then heated for hours, then the solvent is removed in vacuo and the residue is taken up in chloroform. This solution

109817/1971

is first with 2 η hydrochloric acid, then with 10 ^ iger sodium hydroxide solution shaken out, washed until the washing water reacts neutrally and dried over anhydrous calcium sulfate. After removal of the solvent gives a product of the formula

CH ₃ -CO-OC ₂ H ₄ CH ₅ -CO-OC ₂ H

In an analogous manner, starting from 5-N, N-di (β-cyanoethyl) amino aniline the bifunctional coupling compound of the formula

NC-C ₂ H ₄

ⁿ n

NC-C ₂ H

109817/1971

' Example 1.

1.22 parts of the diamine obtained according to regulation IB are dissolved in 50 parts of 2N hydrochloric acid and added to a mixture discharged from 200 parts of ice with 50 parts of glacial acetic acid. Under A solution of 1.6.5 parts of 2-Cvan-4-nitro-aniline is stirred added in 10 parts of In-NitroSylsulfuric acid at 0 °, at 0 ° stirred for 2 hours, the precipitated product filtered off with suction, washed neutral with water and dried. The product of the formula -

Έ ■ ■ N

is a dark powder containing polyester fibers in red Tones of excellent light and sublimation clarity colors.

109817/1 971

Dyeing instructions:

1 part of the dye obtained in Example 1

is with 2 parts of a 50 $ aqueous solution of the sodium salt the dinaphthylmethanedisulphonic acid 'wet ground and dried.

This dye preparation is mixed with 40 parts of a 10 $ aqueous solution of the sodium salt of N-benzyl-μ-heptadecyl-benzimidazole disulfonic acid stirred and 4 parts of a 40% acetic acid solution were added. By diluting a dyebath of 4000 parts is prepared from it with water.

100 parts of a purified polyester fiber material are added to this bath at 50 ° and the temperature is increased within half an hour to 120 to 130 ° and stains for one hour in a closed vessel at this temperature. Afterward is rinsed well. A strong red color of excellent lightfastness and sublimation fastness is obtained.

1098 17/1971

Example 2.

If the diamine obtained according to procedure HB is coupled as in Example 1 with diazotized 2-cyano-4-nitroaniline, this gives the dye of the formula

which dyes polyester fibers in red shades with excellent fastness properties.

10 9 817/1971

Example 3.

If one uses diazotized 4-nitroaniline and proceeds otherwise as indicated in Example 2, the dye of the formula is obtained

which dyes polyester fibers in orange tones

109817/1971

If the diazo components indicated in column I are coupled after diazotization with those in column II
specified coupling components, a dye is obtained which dyes polyester with the shade specified in column III.

III

Eq

.CE

NH—

Red

orange

rub in

Red

orange (color on polyacrylonitrile)

109817/1971

I. cie oh II 2 Il Il C ₀ H, -0-CO-CH, τ ^ Vf ^ t TT ^ * \ / ^ f \ ^ TT ΐττ Il 1 09817/1971 Cl III 2 Q 11
0 9 N
(Y \ -ΝΗ _ρ
CH 0 ^/ ^ ^v S ^/ CH_-N-CH _o -C0- <~~ D
CH ₃ H
I 2 A 1 "Yes. Red Cl
0 ₂ Ν- <$ -ΝΗ ₂ Il 10 6 5 X _{0 Ν}
Il Il
N C-NH ₂ Cl L.
ΊνΓΤΤ —ΓΤ \ .PTT PTT Hm ₂ Orange red brown orange
(Colorations on
Polyacrylonitrile
and on untannier-
ter cotton) CN 0 ₂ Ν- <^ -NH ₂ 1 \ χι UU Uli- OiIp Red 11 O ₂ N- <> -ΝΗ ₂ rub in 12th »Ι i- CH red-violet η \ .α / Ii Il
0 14th 15th

17th

OJSF-

OJt

CN -NH,

-CO-C C-CO- orange

ν- ■ ...- ■

C ₀ H. <—> - _F / 2 4

Cl -NH,

NH-CO-CH ₂ -CH ₀ -

_J 2

Cl

C ₀ H.-CN

NH-CO-CH

Cl -NH,

C ₀ H ₇₁ -CN ²⁴

CH-GH
Il Il
-CO-G C-CO-

NH-CO-CH-CH ₂ -

violet

orange

Red

Red

bordeaux

10981771971

I. CN II CH-CH
Il Il <TI> NH ₂ 2 2 - 2 •1 III 0_N-C / ~ 8H ^ C H-CN ~ -CO-C C-CO- NH-CO-NH-CH ₂ - C _o H.-0-C0-CH "
j Nj ₂ HO-CO-CH ₅ 22nd <> - ^ ^{2 4}
I 2 4
TtTTT 2 NH-CO-NIt- (CH ₂ ) ₅ orange JM Xl H - »2 23 <=> «, 1 Red NH-CO-NEh-CH ₂ It - 24 Cl -
O ₂ H-CI ^ -NH ₂ NH-CO-O-CH ₂ - yellow CN 25th 2 2 orange-
yellow 26th Red 27 violet

109817/1971

I. CN II - · "■.
2 OCH3
. /. H 2 ir 2 ft III 0 _o N- <H> -NH _o <f ~> -r_
"ΛΤΤΤ ft / * \ Λ ^ ΤΤ ■
It. 28 CI ^ -NH ₂ " ¹ Red 0-CH ₂ - •1 CCH ₃ Π 29 IiH-CO-CH ₂ - Red 30th CH ₃ C ₂ S- ^ L ₂ Red orange 31 CN Orange red 32 Cl reddish
blue 33 CN violet 34
I. reddish
blue

1098 17/197 1

III

35

Cl

ojsK> -nh. CH

3
-NH,

NH -CO-CH ₂ -CH ₂ -

Red

36

37

CN -NH,

Cl NH-

NH,

, S- <^ -NH,

- * 0- <~> -NH-C0-NH- <r ~>

rub in

Scarlet fever

38

O.N-

0.N-

CN -HH,

Cl -NH, purple

Red

CN -NH,

-NH,

NH-CO-C-CH ₂ - + -

Red

-W

violet

-0-CO-CH

NH-CO-NH-ιΛ

NH,

9 8 17/1971

II

III

44

O ₂ N-

OJh

CN
-NH,

Cl
-NH,

Cl

CH.

: 6 _o sC-> - ■

-NH,

-CS
0.N— <> NH,

Cl

-NH,

CN

yellow-brown-un

violet

Red

Red

H, C.H, -CN

ruby

C _o H _{/ 1} -0-C0-CH,
• F " ^{2 4}

NH-CO-OC ₂ H ₄

schärlach

bordeaux

109817/1971

II

III

CHSH,

NH-CO-OC ₂ H

GH,

IT

C-NH ₀

O ₀ N-

CN -NH.

C ₂ H ₄ -CN

Cl

cuKZ ^

NH,

-NH,

Cl

> s <z5-m

C ₂ HO-CO-CH. N) ₂ HO-CO-CH.

NH-red

blue

(Coloring on polyacrylonitrile)

rub in

Red

orange

-co-k ^ / '- co-

Ν ·

Scarlet fever

- ¹ 2

CN

OoN-

- <S-NH

^N C ₂ H -CN

NH-

ruby

109817/1971

Example 56. Continuous dyeing of polyester fabric,

20 parts of the dye of the formula

NH-CC-CH,

be with 140 parts of water, which 40 parts of dinaphthylmethandisulfonsaures Contains sodium, grind.

A padding liquor is prepared from 200 parts of the above dye preparation, 100 parts of carboxymethyl cellulose (4 $ aqueous solution) and 700 parts of water by adding the dye preparation described above using a Schnell-r stirrer stirs into the prediluted thickening and the Then adjust the mixture to a pH value of 6 with 80% acetic acid. In this liquor there is a fabric made of polyester fibers at JO and with a squeeze effect padded from $ 60 and then dried at 70 to 80 ° The fabric is then placed on the stenter for 60 seconds 210 heated and then washed hot and well rinsed with cold water. A fabric is obtained which is colored violet with good fastness properties.

109817 / 1971-

- 84 -

Example 57. 1 part of the dye of formula

CH.

CH-N-CH ₂ -GC

-N = N

■ Ν (C ₂ H ₄ -O-CO-CH ₅ ) ₂

NH-CO-

CH-CH

-C C-

becomes 40% in 5000 parts of water with the addition of 2 parts Acetic acid dissolved. 100 parts of dried polyacrylonitrile staple fiber yarn are added to this dyebath at βθ one, increases the temperature to 100 within half an hour and colors one hour at boiling temperature. then the dye is rinsed well and dried. The result is an orange coloration with very good light, sublimation and Washfastness.

109817/1971

Claims (1)

- 35 - Claims. 1. Diazo compounds in which two monoazo color substance molecules of the general type DN = NAN ^L - wherein D is the radical of a mono- or bicyclic diazo component, A is a p-phenylene radical, and L and R_ are each an alkyl radical their coupling components by a divalent bridge Z are linked without coloring agent character, with at least one of the monoazo dye radicals directly on the aromatic nucleus A, optionally via a nucleus-bound alkylene bridge, with the divalent radical Z is linked, and the group Z if D represents a heterocyclic system and Z represents two directly with the "phenylene radicals A or two oxygen atoms connected directly to the phenylene radicals via the nitrogen atom A contains linked carboxamide groups, equal to | at the time either an unsaturated, aromatic or heterocyclic one Contains radical or a carbon chain interrupted by at least one heteroatom. 2. New disazo compounds of the formula 109817/1971 ^N E — A ₂ —N = JSh- D _n -N = NA ■ i Alkylenf q-1 x-1 ■ (alkylene wherein R, R, R_ and R ₁ , each a hydrogen atom or preferably alkyl groups, where, when x = 2, Rp can be connected to the radical A _p to form a ring, R '^ an alkylene group, q, r and χ each an integer in the value of 1 or 2, A and Ap each represent a phenylene radical on which the azo group and the group -NR, R ^ or -NRpR ₁ , are in the 1,4-position to one another, D and / or D _p each denotes the remainder of an optionally quaternized diazo component and Z denotes a divalent bridge member without dye character, where when x = l, q = l and r = l and the residues D and D _? each represent a heterocyclic system and Z two oxygen atoms connected _{directly to the aromatic radicals A and A p or two via} 10 9817/197 1 the nitrogen atom contains linked carboxamide groups, the pontic Z at the same time is either an unsaturated / aromatic or heterocyclic radical or a through Contains at least one heteroatom interrupted carbon chain. J5. Disazo compounds according to claim 2 / characterized in that at least one radical, preferably both radicals, of the diazo components of the formulas D and D are not heterocyclic Ring and / or contains no quaternizable or no quaternized heteroatoms, and that the dyes contain no sulfo groups. 4. disazo compounds according to claim 3, characterized in that at least one radical, preferably both radicals of the diazo components of the formulas D and D are quaternized are, and that the dyes are not free sulfonic acid or Contain carboxyl groups. · 5. disazo compounds according to claims 3 and 4, characterized characterized in that the diazo radicals D and D_ are a benzene radical with negative substituents or a heterocyclic radical 6. disazo compounds according to claim 5, characterized in that the divalent bridge Z contains at least one heteroatom. 7 · disazo compounds according to claim 6, characterized in that the divalent bridge Z is at least one 109817/1971 Contains acyl group. 8. disazo compounds according to claim J, characterized in that the divalent bridge Z contains an acyl group. 9. disazo compounds according to claim 8, characterized in that that the divalent bridge Z is an oxycarbonylamino group or aminocarbonyloxy group. ™ 10. disazo compounds according to claim 8, characterized in that that the divalent bridge Z contains a urea residue. 11. disazo compounds according to claim 8, characterized in that the divalent bridge Z is an oxycarbonyloxy group contains. 12. Disazo compounds according to claim ¹ J, characterized in that the divalent bridge Z contains at least 2 acyl groups or as connecting divalent groups in the main chain which connects the azo dye residues to one another. 1 ^ - disazo compounds according to claim 8, characterized in that that Z is a residue of the formula denotes in which X ^{1 is} an oxygen atom, a sulfur atom or an imino group and Z ^{1 is} the diacyl radical of an organic bifunctional acid. 10981 7/197 1 Λ Λ .89 -; ■■ l4. Disaζο compounds according to claim 13, wherein Z. ' the diacyl radical of an aliphatic, cycloaliphatic ^ arali phatic, aromatic or heterocyclic dicarboxylic acid 15 disazo compounds according to claim 1J5, wherein Z ' the diacyl radical of an aliphatic, cycloaliphatic ^ arali phatic, aromatic or heterocyclic dicarbamic acid. ; l6. Disazo compounds according to claim IJ, in which Z 'is the diacyl radical of an aliphatic or aromatic disulfonic acid. If. Disazo compounds according to claim 12, characterized in that that Z is a residue of the formula means where R- is a divalent organic radical, and X 'is an oxygen atom or a sulfur atom, and at least one of the radicals D, and D "a negatively substituted-" is ated benzene residue. 18. Process for the preparation of disazo compounds, characterized in that either a) two coupling components A- »N ^ 1, which is connected by a two-valued bridge Z ■ ■■ - ■ '. ^"R 2 .-: ^-: ■ are connected to each other without dye-character and of which at least one directly to the." Aromatic nucleus A, optionally bonded via an alkylene bridge core bonded to the radical Z is, with diazo compounds of amines 109817/1971 - gio - and D-NHp couples to disazo compounds, the Symbols A, Z, R, Rp, D and D have the meaning given above have, or that one b) two identical or different dyes of the formula R. wherein D and R have the meaning given, A one 1,4-phenylene radical and R., an optionally substituted Alkyl group or a hydrogen atom and where in one of the radicals A and R_ a convertible substituent is present, reacts with the compounds donating the radical Z at the same time in one stage or successively in two stages. 19. Process for the preparation of disazo compounds of the formula. -A ₁ falkylene ) - (Alkyl ₉ -N = ND 10 9 8 17/1971 - 9i - wherein R, R _p , R_ and R ₂ , each a hydrogen atom or preferably alkyl groups, where, when x = 2, R_ can be connected to the radical A ₂ to form a ring, R ¹ ^. an alkylene group, q, r and χ each an integer in the value of 1 or 2, A and Ap each a phenylene radical on which the azo group and the group -NR R ₁ or -NRpR ₁ . are in 1,4-position to one another, D and / or D. each denotes the remainder of an optionally quaternized diazo component and Z denotes a divalent bridge member without dye character, where when x = l, q = l and r = l and the radicals D and D_ each represent a heterocyclic system and Z contains two oxygen atoms directly connected to the aromatic radicals A and Ap or two carboxamide groups connected via the nitrogen atom, the bridge member Z at the same time either an unsaturated, aromatic or heterocyclic radical or a carbon chain interrupted by at least one heteroatom contains, characterized in that one m_ - (alkylene) 1-1 - ^E 4 -H x-1 - (alkylene) -A ₂ -H N - 2-x 109817/1971 wherein Α _χ , A _g , R ₁ , R ₂ , RR ^, R ¹ ^, Z, r, q and χ have the same meaning as above. LN = N ¹ A ₁ N / 1 | 1 \ _R Via (alkylene) X ₁ ■ A D ₉ -N = NA ₉ -N ^ I (alkylene) ι "- ¹ ₉ N = NA ₅ N ² 2 \, _ "VIc D ₉₅ ^K 4 wherein X- and X _p each contain at least one reactive atom-containing groups, such as a carboxyl or sulfonic acid group or their acid halide groups, or a mobile halogen atom, or an acylatable group, such as, in particular, an amino, mercapto or hydroxyl group, or their reactive derivatives represent, and R, R ", R 1, R ^, R \, A ,, Ap, D, D, q and r have the same meaning as above, with the bifunctional compound Z ¹ , which at the condensation with the groups X, and Xp forms the bridge member Z, condense to form the dyes of the formula (II) according to the invention or 10981 7/197 Azo dyes of the formulas D ₁ -N = N -A _n --- (alkylene) - X ₁ I ¹ D ₂ -N = NA ₂ ^ - (alkylene) - ^ - N
R ₂ ^R 4 or τ> D ^ -N = NA ₀ - where D, Dp, A ,, A _? , R, R, R. ,, R _2. , R'u, q and r have the same meaning as above and X-. and X _p each denotes a group which is reactive towards addition-capable double bonds or oxirane rings and contains at least one active hydrogen atom, to a bifunctionally addition-capable compound of the formula Y -Z-Yp wherein Y-. and Y. each have an additive- ' Remainder of the formulas -CH = CH ₂ or -CH ₂ -CH ₂ , anneal, or the azo dyes of the formulas Via, VIb or VIg, in which X ₁ and X ₂ each represent an SH group, oxidize to disazo dyes and, if appropriate, the disazo dyes obtained on at least one of the radicals D. or D _? quaternize if these contain quaternizable groups, or else optionally in the coupling with the bifunctional azo component 10 9817/1971 already used at least a molar proportion of already quaternized Diaζoniumverbindungen. 20. The method according to claim 19, characterized in that that the bifunctionally reactive compound of the formula Z 'is an acylating agent which is the radical of a divalent introduces organic acid, and the groups X and Xp each represents an amino, mercapto or, preferably, hydroxyl group A represent. 21. The method according to claim 20, characterized in that the acylating agent is a dihalide of an organic Is dicarboxylic acid. 22. The method according to claim 20, characterized in that the acylating agent is a diisocyanate. 2Y. Method according to claim 20, characterized in that that the acylating agent is phosgene. 24. The method according to claim I9, characterized in that "that the multifunctional compound of the formula is a diepoxyd. 25. The method according to claim 19, characterized in that that one is a monoazo compound of the formula 10 9 817/1971 ^R 2
(alkylene) OH D ₀ N = NA ₀ GH with phosgene to form a chlorocarbonic acid ester and the resulting ester with an equivalent amount of a monoazo dye of the formula R, -N = NA JS / (alkylene). ι q-1 wherein X 'is a hydroxyl, mercapto, or primary or secondary amino group, condensed. 26. The method according to claim 19, characterized in that that a bifunctional coupling component is used, in which Z contains at least one acyl radical. 2! J. Process according to claim 26, characterized in that the acyl radical is derived from carbonic acid. 109817/1971 28. The method according to claim 26, characterized in that that the acyl radical is a radical of a dicarboxylic acid. 29 · Disazo compounds as described in the examples. 30. Dye preparations, which one of the claims Contain 1 to 17 claimed dyes. 31. Process for dyeing synthetic fiber materials,
characterized in that dyestuffs according to Claim 1 are used. 32. A method for dyeing or printing synthetic fibers, in particular polyester fibers, which thereby
characterized in that one is preferably of carboxyl and
Disazo dyes of the formula which are free from sulfo groups D ₁ -N = NA ₁ (alkylene) - = - Z- -L ι ± C [-J_ —A_ — K = N — D
² x-1 - (alkylene) 10 9 817/1971 -97 -, ■■■■■; where R ,, Rp, R ^ and Rj, each a hydrogen atom or preferably V alkyl groups, where, when x = 2, R _{p can be} connected to the radical A_ to form a ring, R'j, an alkylene group, q, r and χ each an integer in the value of 1 or 2, A, and Ap each a phenylene radical on which the azo group and the group -NR ₁ R-, or NR R ₂ , are in the 1,4-position to one another, D and / or D each denotes the remainder of an optionally quaternized diazo component and Z denotes a divalent bridge member without parabellum character, their mixtures with one another and their mixtures with other azo dyes, in particular monoazo dyes, are used. 33 · Process for dyeing and printing synthetic Pasern, in particular of polyester fibers, characterized by the use of the dyes according to claims 2 and 3 to 17 · 3Ϊ. The colored material obtained according to claim 32. 35 · Process for pigmenting high molecular weight organic Material, characterized by the use of water-insoluble dyes according to claims 1, 2 and 4 to 16. 36. Process for dyeing synthetic fiber-forming Polymers such as polyesters, polyolefins or polyamides in the spinning solution, with dyes according to claims 2, 4 to 17. 37 · The colored material obtained according to claim 36. 38. -Process for dyeing acrylic fibers, characterized through the use of quaternized dyes according to claims 3 to 17. 1 0 9 8 1 7/1 9 7 1 - 9B - The colored material obtained according to claim J> Q Dinitro compounds of the formula ON-A - (alkylene) Z ^N N x-1 -NO, 2-x in which R, B., R and RV are hydrogen atoms or preferably optionally substituted alkyl groups, q and r are each an integer of 1 or 2, χ but preferably 1, Z is a colorless bridge member, preferably a divalent radical, preferably interrupted by at least one heteroatom , which contains at least one, preferably at least two acyl groups or a diacyl radical as divalent groups in the main chain, and HA and HA ₂ each represent a phenylene radical which each carries a hydrogen atom in the para position to the nitro group. 10 9 8 17/1971 41, - 99 - Diamines of the formula A ₁ - (alkylene) —Z- ^R 3 * 4 A. ν x-1 - (Alkylene) -A ₉ -NR ₀ R r-1 ^ 2-x where R-, R_, Rz and Ffyi "are hydrogen atoms, or preferably optionally substituted alkyl groups, R ¹ κ is an alkylene group, x, q and r are each an integer of 1 or 2, Z is preferably interrupted by at least one heteroatom colorless bridge link, in particular a divalent radical which contains at least one, preferably at least two acyl groups or a diacyl radical as divalent groups in the main chain, and HA and A-Ap each represent a para-phenylene radical which is in the para position to the group -NR ₁ R ^ or -NR ₉ Rh each carries a hydrogen atom. 42. Amines of the formula NH. C 1 -alkylene -— Τ _Ί ^N G ₂ _ ₃ -alkylene-Y ₂ 109817/1971 where Y and Y_ each have a hydroxyl, acyloxy, acylamino or cyano group and D a hydrogen atom, an alkyl or alkoxy group with 1 to 2 carbon atoms or a halogen atom, especially a chlorine atom. 4 ^. Amines according to claim J59 *, characterized in that Y and / or Y is an aliphatic or aromatic m acyloxy radical. 44. amines according to claim 39, characterized in that that Y and / or Y represents a cyano group. 109817/1971